Photopolymerizable composition based on a vinyl compound, a sulfur-containing compound and an alpha-diketone

ABSTRACT

A photopolymerizable composition comprising a vinylic compound, a sulfur-containing compound and an α-diketone is disclosed. The sulfur-containing compound may be a mercaptobenzoic acid or a polysulfide.

This is a division of application Ser. No. 765,925, filed Aug. 15, 1985, now U.S. Pat. No. 4,777,190.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to photopolymerizable compositions comprising a vinylic compound, a sulfur-containing compound and an α-diketone.

2. Discussion of the Background

Photopolymerization is used in various fields. For example, print materials, photosensitive agents used in reproduction, printed wirings, integrated circuits, and image formation for precision fabrication, such as shadow masks, as well as paints, printing inks and adhesives, all rely on photopolymerization.

Photopolymerization is also used in dentistry, for example, photopolymerizable materials are used in association with tooth fillers (composite resins or the likes), tooth sealing materials and dental adhesives, as well as in the production of tooth decay preventive fillers, tooth crowns and dentures

A case in point with regards to the photopolymerizable compositions described above, is a photopolymerizable composition curable with visible light or UV-rays described in Japanese Patent Publication No. 10986/1979. This photopolymerizable composition comprises a photosensitive catalyst containing a photosensitive agent/reducing agent as the photo-initiator. This photo-initiator is made up of components (a) and (b). Component (a) has at least one photosensitive agent represented by the following formula: ##STR1## where;

X represents >C=0, >CR₅ R₆ or >CR₇ OR₈ ; and R₅ -R₈ may be either identical or different and each represents a hydrogen or a hydrocarbon group; n is 0 or 1; and the groups A which may be either identical to each other or different from each other represent an unsubstituted hydrocarbon group or a substituted hydrocarbon group. Both of the groups A may be coupled directly, joined by way of a bivalent hydrocarbon group, or alternatively, both of the groups A may form together a condensed aromatic ring. The group A may represent an unsubstituted aromatic group or a substituted aromatic group if n is 1 and X is >CR₅ R₆ and if n=0. Component (b) has at least one reducing agent represented by the formula:

    NRRR

where each R may be identical or different with respect to each other; and each R represents a hydrogen, an unsubstituted hydrocarbon group, a substituted hydrocarbon group or a group in which two R form a ring together with N. Three R do not simultaneously represent substituted hydrocarbon groups and N is not coupled directly to the aromatic group. The photopolymerizable composition also contains an unsaturated polymerizable ethylenic material. Particularly preferred examples of this unsaturated polymerizable ethylenic material, for the photosensitive agent are: biacetyl, benzil, benzophenone, camphorquinone and the like. For the reducing agent preferred examples are: trimethylamine, tripropylamine, dimethylamine, propylamine, N,N'-dimethylaniline, N-methyldiphenylamine, ethylenediamine, hexamethylenediamine, dimethylaminoethyl methacrylate, piperidine and the like.

Although the materials using these photoinitiators can be rapidly cured via photoirradiation, they suffer several drawbacks. The curing products are significantly colored (mostly yellowed), they show significant aging (i.e. change in color tone) upon exposure to sunlight or water, and products with low strength are produced.

Accordingly there is a particular need for a novel photopolymerization composition which may have wide application and which does not suffer from the drawbacks outlined above.

SUMMARY OF THE INVENTION

Accordingly it is an object of this invention to provide a novel photopolymerizable composition which provides excellent products, free from undesirable coloration.

It is another object of this invention to provide a novel photopolymerizable composition which is not subject to aging (i.e. change in color tone) upon exposure to sunlight or water.

It is another object of this invention to provide a novel photopolymerizable composition which provides products having excellent mechanical properties.

It has now been surprisingly discovered that a photopolymerizable composition comprising a vinylic compound, a sulfur-containing compound and an α-diketone meets all of the objects of this invention outlined above. The sulfur-containing compound may be a mercaptocarboxylic acid or a polysulfide.

Accordingly this invention relates to a novel photopolymerizable composition comprising a vinylic compound, a mercaptocarboxylic acid and an α-ketone. This invention also provides a novel photopolymerizable composition comprising a vinylic compound, a polysulfide and an α-diketone. In this photopolymerizable composition the sulfur-containing compound (i.e. the mercaptocarboxylic acid or the polysulfide) and the α-diketone are photopolymerization initiators.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This invention thus relates to a novel photopolymerizable composition which comprises a vinylic compound, a sulfur-containing compound and an α-diketone.

In a preferred embodiment of this invention, the photopolymerizable comprises a vinylic compound, a mercaptocarboxylic acid and an α-diketone, or the photopolymerizable composition comprises a vinylic compound, a polysulfide and an α-diketone.

In another preferred embodiment of this invention, the photopolymerizable composition may additionally contain a filler well known in this art.

In another preferred embodiment of this invention, the photopolymerizable composition contains a mercaptocarboxylic acid compound represented by one of the formulae below: ##STR2## wherein

R₁ and R₂ independently may be a C₁₋₅ alkylene group or a phenylene group; and

R₃ may be a nitro group, a hydroxyl group, an amino group or a halogen atom.

In another preferred embodiment of this invention, the α-diketone may be camphorquinone.

In another preferred embodiment of this invention, the mercaptocarboxylic acid may be orthomercaptobenzoic acid (i.e. thiosalicylic acid), metamercaptobenzoic acid or para-mercaptobenzoic acid.

In another preferred embodiment of this invention, the polysulfide may be a compound represented by the following formula:

    R.sub.4 --S--(--S--).sub.n --S--R.sub.4

wherein

n is an integer of from 0 to 10;

R₄ is either a saturated or an unsaturated C₁₋₂₀ alkyl group, a phenyl or a benzyl group, each of which may be either unsubstituted or substituted with a carboxylic group at any position.

The vinylic monomer constituting the composition of this invention may either be a mono-functional vinylic compound or a poly-functional vinylic compound. Examples of mono-functional vinylic compound can include styrene, acrylonitrile, vinyl acetate, methyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, methacryloxyethyl trimellitic acid or an acid anhydride thereof. Examples of the polyfunctional vinyl compounds can include, for example, those represented by the formula: ##STR3## where;

R₉ is a hydrogen atom or a methyl group and p is an integer of from 1 to 20. The polyfunctional vinylic compound, may be, for example, ethylene glycol di-acrylate or methacrylate, diethylene glycol di-acrylate or methacrylate, triethylene glycol di-acrylate or methacrylate, polyethylene glycol di-acrylate or methacrylate, 1,4-butanediol di-acrylate or methacrylate, 1,3-butanediol di-acrylate or methacrylate, 1,6-hexanediol di-acrylate or methacrylate and glycerine di-acrylate or methacrylate. Other examples of the polyfunctional vinylic compound are represented by the formula: ##STR4## where;

R₁₀ is a hydrogen atom or a methyl group; and p is an integer of from 1 to 20. Examples of these polyfunctional vinylic compounds are: bisphenol A digylcidyl acrylate or methacrylate, urethane di-acrylate or methacrylate, trimethylolpropane tri-acrylate or methacrylate, pentaerythritol tetraacrylate or methacrylate, bisphenol A di-acrylate and methacrylate. These acrylates and methacrylates may be used alone or as a combination of two or more.

The mercaptocarboxylic acid used as the photopolymerization initiator in this invention is a compound, preferably, represented by the following formulae: ##STR5## where:

R₁ and R₂ each are a C₁₋₅ alkylene group; or a phenylene group;

R₃ is a nitro group, an oxy group, an amino group or a halogen atom. Specific examples can include, for example, o-, m- and p-mercaptobenzoic acid, o-, m- and p-mercaptophenyl acetic acid, o-, m- and p-mercaptophenyl propionic acid, o-, m- and p-mercaptophenyl butyric acid, mercaptobiphenyl carboxylic acid, o-, m- and p-mercaptomethyl benzoic acid, o-nitro-p-mercaptobenzoic acid, o-hydroxy-p-mercaptobenzoic and, o-amino-p-mercaptobenzoic acid and o-chloro-p-mercaptobenzoic acid. Particularly preferred mercaptocarboxylic acid can include, for example, o-mercaptobenzoic acid (thiosalicylic acid), m-mercaptobenzoic acid and p-mercaptobenzoic acid.

While all sorts of α-diketones may be used with no particular restriction, preferred α-diketones are camphorquinone benzyl, acetylbenzoyl, acenaphenequinone, α-naphthyl, dichlorobenzyl, biacetyl, β-naphthyl, benzoin, α-naphthoin and β-naphthoin. Among all, camphorquinone is most referred.

The polysulfide used as the photopolymerization initiator in this invention is a compound, preferably, represented by the following formula:

    R.sub.4 --S--(S).sub.n --S--R.sub.4

where;

n is an integer from 0 to 10;

R₄ is a saturated or unsaturated C₁₋₁₀ alkyl group, a phenyl or a benzyl group, each of which may be unsubstituted or substituted with a carboxylic group at any position. Specific examples can include, for example, dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, diphenyl disulfide, dibenzyl disulfide, trimethylene disulfide, dimethyl trisulfide, diethyl trisulfide, dipropyl trisulfide, dibutyl trisulfide, diphenyl trisulfide, dibenzyl trisulfide, p-(phenyl disulfanil) benzoic acid and 3,3'-trithiodipropionic acid. Particularly preferred polysulfide can include, for example, diphenyl disulfide, dibenzyl disulfide, di-t-butyl disulfide, trimethylene disulfide, p-(phenyl disulfanil) benzoic acid, diphenyl trisulfide and dibenzyl trisulfide.

The photopolymerization initiator is added in an amount from 10⁻⁵ % by weight to 30% by weight, preferably, from 10⁻³ % by weight to 15% by weight and, most preferably, from 10⁻¹ to 5% by weight based on the vinylic monomer. Further, the blending amount of the α-diketone lies within a range form 10⁻⁵ % by weight to 10² % by weight, preferably, from 10⁻³ % by weight to 50% by weight and, most preferably, from 10⁻¹ % by weight to 20% by weight based on the mercaptocarboxylic acid. These blending amounts are preferred for obtaining a composition free from coloration and aging color change in the photopolymerization curing products, and for products with high mechanical strength.

In the composition according to this invention, a filler may further be added as required to the ingredients as described above. Preferred filler ingredient can include oxides, hydroxides, chlorides, sulfates, sulfites, carbonates, phosphates, silicates of metals belonging to the groups I, II, III, IV and V of the Periodic Table and transition metals, as well as mixture and composite salts thereof. Silicon dioxide, quartz powder, aluminum oxide, barium sulfate, titanium oxide, talc, glass powder, glass beads, glass fibers, glass fillers containing barium salt and lead salt, silica gel, colloidal silica, carbon fibers, zirconium oxide, tin oxide and other ceramic powder are particularly preferred. As the filler, any non-treated fillers, fillers surface-treated with silane coupling agents or the likes and those organic composite fillers composited with a polymer and pulverized may also be used.

While the blending amount of the filler may properly be varied depending on the purpose of use of the photopolymerization curing products, it is blended within a range from 1 to 10³ % by weight, preferably, from 10 to 9.5×10² % by weight and, particularly preferably, from 20 to 9.0×10² % by weight based on the vinylic monomer as described above. The composition may be served as a paste-like, for example, when it is used in dental filler application.

Furthermore, the composition according to this invention may also be blended as required with colorants, polymerization inhibitors (for example, hydroquinone, methoxybenzophenone, methylphenol, hydroquinonemonomethyl ether), oxidation stabilizers, UV absorbers (for example, benzophenone), pigments (for example, iron oxide, and titanium oxide), dyes and the like.

In the photopolymerizable composition according to this invention, since a photopolymerization initiator capable of curing by visible light radiation is used, it does not suffer the problems of prior UV-ray photopolymerization, compositions. Human toxicity, poor curing performance (depth) and expensive installation cost are all absent. Further, the curing products obtained by photocuring have an excellent color stability, a very pleasant appearance and high mechanical properties, none of which could be obtained by the prior process.

Other features of this invention will become apparent in the following descriptions of exemplary embodiments which are given for illustration of the invention and are not intended to be limiting thereof.

EXAMPLES 1-3, COMPARATIVE EXAMPLES 1-2

A monomer mixture comprising:

2,2-bis(4-(3-methacryloxy-2-hydroxypropoxy)phenyl)propane hereinafter simply referred to as Bis-GMA): 4 g

Triethyleneglycol dimethacrylate (hereinafter simply referred to as 3G): 6 g

Photopolymerization initiator (Compounds and the addition amount listed in Table 1) was poured into a teflon tube (4 mm inner diameter, 20 mm height), sealed at the bottom until the upper surface of the solution was level with the upper surface of the teflon tube. The teflon tube was disposed such that the liquid level was situated at a 1 mm distance from the light irradiation surface of a visible light irradiator (manufactured by 3M Corporation, Trade name: OPTILUX) and visible rays were irradiated for 30 seconds. The poured monomer mixture was recovered from the teflon tube, removed with a non-polymerized portion, and the "thickness" was measured for the thus obtained polymerization curing product.

Table 1 shows the kind and the amount of the photoinitiator, as well as the result for measurement of the foregoing "thickness".

                  TABLE 1                                                          ______________________________________                                                              Addition   Thick-                                                              amount (%) ness                                                                (based on  measured                                              Photoinitiator                                                                               monomer)   (mm)                                           ______________________________________                                         Example 1                                                                               thiosalicylic acid                                                                             3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Example 2                                                                               m-mercaptobenzoic acid                                                                         3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Example 3                                                                               p-mercaptobenzoic acid                                                                         3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Comparative                                                                             camphorquinone  0.05         4.0                                      Example 1                                                                      Comparative                                                                             N,N'-dimethylanyline                                                                           3.0          13.8                                     Example 2                                                                                  +                                                                           camphorquinone  0.05                                                  ______________________________________                                    

As apparent from Table 1, the compositions according to this invention have an excellent photocuring performance as compared with the known compositions of the comparative examples. Furthermore, the photocuring polymerizates according to this invention suffered no substantially coloration, and were remarkably finer as compared with that of the comparative examples.

EXAMPLES 4-6, COMPARATIVE EXAMPLES 3-4

A monomer filler mixture (paste) comprising:

Bis-GMA: 0.8 g

3G: 1.2 g

Silane modified quartz powder: 8 g

Photopolymerization initiator (Compounds and the addition amount listed in Table 2) was packed into a teflon tube (4 mm inner diameter, 20 mm height) sealed at the bottom until the upper surface of the paste was level with the upper surface of the teflon tube. The teflon tube was disposed such that the paste surface was situated at a 1 mm distance from the light irradiation surface of a visible light irradiator manufactured by 3M Corporation, Trade name: OPTILUX) and visible rays were irradiated for 30 seconds. The packed paste was recovered from the teflon tube, removed with a not-polymerized portion and the "thickness" was measured for the thus obtained polymerization curing product.

Table 2 shows the kind and the amount of the photoinitiator, as well as the result for measurement of the foregoing "thickness".

                  TABLE 2                                                          ______________________________________                                                              Addition   Thick-                                                              amount (%) ness                                                                (based on  measured                                              Photoinitiator                                                                               monomer)   (mm)                                           ______________________________________                                         Example 4                                                                               Thiosalicylic acid                                                                             3.0        12.0                                                   +                                                                           camphorquinone  0.05                                                  Example 5                                                                               m-mercaptobenzoic acid                                                                         3.0        11.5                                                   +                                                                           camphorquinone  0.05                                                  Example 6                                                                               p-mercaptobenzoic acid                                                                         3.0        12.0                                                   +                                                                           camphorquinone  0.05                                                  Comparative                                                                             camphorquinone  0.05        1.2                                       Example 3                                                                      Comparative                                                                             N,N-dimethylaniline                                                                            3.0         5.6                                       Example 4                                                                                  +                                                                           camphorquinone  0.05                                                  ______________________________________                                    

As apparent from Table 2, the compositions according to this invention have an excellent photocuring performance also in the case where the filler is added as compared with the known compositions of the comparative examples. Furthermore, the photocuring polymerizate according to this invention suffered no substantial coloration, and were remarkably finer as compared with that of the comparative examples.

COMPARATIVE EXAMPLE 5

After pouring each of the compositions corresponding to examples 1 and 4 respectively into the above-mentioned teflon tube, the upper surface of teflon tube was covered with an aluminum foil so that visible rays could not reach the poured mixture. Then, the tube was disposed such that the upper surface of the poured mixture was at a 1 mm distance from the light irradiation surface and visible rays were irradiated for 3 minutes by no polymerization took place.

COMPARATIVE EXAMPLE 6

After pouring each of the compositions, corresponding to Examples 1 and 4 respectively into the above-mentioned teflon tube, the upper surface of teflon tube was covered with an aluminum foil so that visible rays could not reach the poured mixture. Then, the tube was heated for 3 minutes at 60° C. but no polymerization took place.

EXAMPLES 7-9, COMPARATIVE EXAMPLE 7-9

A monomer filler mixture (paste) comprising:

Bis-GMA: 0.8 g

3G: 1.2 g 3G: 1.2 g

Silane modified quartz powder: 7 4 g

Silicon dioxide fine powder: 0.6 g

Photopolymerization initiator (Compound and the addition amount listed in Table 3) was irradiated with visible rays for 60 seconds under the same procedures as those in Example 4. Then, the thus obtained photopolymerization curing products were cut into cylindrical specimens each of 4×6 mm, for which measurement was made to the compression strength, color change after exposure test to sunlight for one week and color change after one week immersion test in water at 60° C.

Table 3 shows the kind and the amount of the photoinitiator, as well as the results of the above-mentioned measurement.

                                      TABLE 3                                      __________________________________________________________________________                                                Color change                                                                             Color change after                             Addition amount (%)                                                                       Compression strength                                                                      one week exposure                                                                        one week immersion                Photoinitiator                                                                              (based on monomer)                                                                        (kg/cm.sup.2)                                                                             to sunlight                                                                              in water at                                                                    60° C.             __________________________________________________________________________     Example 7                                                                              thiosalicylic acid +                                                                        3.0        2950       none      none                              camphorquinone                                                                              0.05                                                      Example 8                                                                              m-mercaptobenzoic acid +                                                                    3.0        2750       "         "                                 camphorquinone                                                                              0.05                                                      Example 9                                                                              p-mercaptobenzoic acid +                                                                    3.0        2800       "         "                                 camphorquinone                                                                              0.05                                                      Comparative                                                                            camphorquinone                                                                              3.0        1460       extremely great                                                                          extremely great           Example 7                                                                      Comparative                                                                            N,N'-dimethylaniline +                                                                      3.0        1780       "         "                         Example 8                                                                              camphorquinone                                                                              0.05                                                      Comparative                                                                            5-butylbarbituric acid +                                                                    3.0        1800       great     great                     Example 9                                                                              camphorquinone                                                                              0.05                                                      __________________________________________________________________________

As apparent from Table 3, the compositions according to this invention have excellent mechanical strength and extremely high color stability as compared with the known compositions of the comparative examples.

EXAMPLES 10-16, COMPARATIVE EXAMPLES 10-11

A monomer mixture comprising:

2,2-bis(4-(3-methacryloxy-2-hydroxypropoxy)phenyl)propane (hereinafter simply referred to as Bis-GMA): 4 g

Triethyleneglycol dimethacrylate (hereinafter simply referred to as 3G): 6 g

Photopolymerization initiator (Compounds and the addition amount listed, in Table 4) was poured into a teflon tube (4 mm inner diameter, 20 mm height) sealed at the bottom until the upper surface of the solution was level with the upper surface of the teflon tube. The teflon tube was disposed such that the liquid level was situated at a 1 mm distance from the light irradiation surface of a visible light irradiator (manufactured by 3M Corporation, Trade name: OPTILUX) and visible rays were irradiated for 30 seconds. The poured monomer mixture was recovered from the teflon tube, removed with not-polymerized portion and the "thickness" was measured for the thus obtained polymerization curing product.

Table 4 shows the kind and the amount of the photo initiator, as well as the result for measurement of the foregoing "thickness".

                  TABLE 4                                                          ______________________________________                                                              Addition   Thick-                                                              amount (%) ness                                                                (based on  measured                                              Photoinitiator                                                                               monomer)   (mm)                                           ______________________________________                                         Example 10                                                                              diphenyl disulfide                                                                             3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Example 11                                                                              dibenzyl disulfide                                                                             3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Example 12                                                                              di-t-butyl disulfide                                                                           3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Example 13                                                                              trimethylene disulfide                                                                         3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Example 14                                                                              p-(phenyldisulfanil)                                                                           3.0        more                                                benzoid acid               than                                                   +                       20                                                  camphorquinone  0.05                                                  Example 15                                                                              diphenyl trisulfide                                                                            3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Example 16                                                                              dibenzyl trisulfide                                                                            3.0        more                                                   +                       than                                                camphorquinone  0.05       20                                         Comparative                                                                             camphorquinone  0.05         4.0                                      Example 10                                                                     Comparative                                                                             N,N'-dimethylaniline                                                                           3.0          13.8                                     Example 11                                                                                 +                                                                           camphorquinone  0.05                                                  ______________________________________                                    

As apparent from Table 4, the compositions according to this invention have an excellent photocuring performance as compared with the known compositions of the comparative examples. Furthermore, the photocuring polymerizates according to this invention did not suffer substantial coloration, and were remarkably finer as compared with the comparative examples.

EXAMPLES 17-23, COMPARATIVE EXAMPLES 12-13

A monomer filler mixture (paste) comprising:

Bis-GMA: 0.8 g

3G: 1.2 g

Silane modified: 8 g

Photopolymerization initiator (Compounds and the addition amount listed in Table 5) was packed into a teflon tube (4 mm inner diameter, 20 mm height) sealed at the bottom until the upper surface of the paste was level with the upper surface of the teflon tube. The teflon tube was disposed such that the paste surface was situated at a 1 mm distance from the light irradiation surface of a visible light irradiator (manufactured by 3M Corporation, Trade name: OPTILUX) and visible rays were irradiated for 30 seconds. The packed paste was recovered from the teflon tube, removed with a non-polymerized portion and the "thickness" was measured for the thus obtained polymerization curing product.

Table 5 shows the kind and the amount of the photoinitiator, as well as the result for measurement of the foregoing "thickness".

                  TABLE 5                                                          ______________________________________                                                              Addition   Thick-                                                              amount (%) ness                                                                (based on  measured                                              Photoinitiator                                                                               monomer)   (mm)                                           ______________________________________                                         Example 17                                                                              diphenyl disulfide                                                                             3.0        13.0                                                   +                                                                           camphorqinone   0.05                                                  Example 18                                                                              dibenzyl disulfide                                                                             3.0        11.1                                                   +                                                                           camphorquinone  0.05                                                  Example 19                                                                              di-t-butyl disulfide                                                                           3.0        12.5                                                   +                                                                           camphorquinone  0.05                                                  Example 20                                                                              trimethylene disulfide                                                                         3.0        10.6                                                   +                                                                           camphorquinone  0.05                                                  Example 21                                                                              p-(phenyl disulfanil)                                                                          3.0        12.0                                                benzoid acid                                                                      +                                                                           camphorquinone  0.05                                                  Example 22                                                                              diphenyl trisulfide                                                                            3.0        10.9                                                   +                                                                           camphorquinone  0.05                                                  Example 23                                                                              dibenzyl trisulfide                                                                            3.0        12.8                                                   +                                                                           camphorquinone  0.05                                                  Comparative                                                                             camphorquinone  0.05        1.2                                       Example 12                                                                     Comparative                                                                             N,N'-dimethylaniline                                                                           3.0         5.6                                       Example 13                                                                                 +                                                                           camphorquinone  0.05                                                  ______________________________________                                    

As apparent from Table 5, the compositions according to this invention have an excellent photocuring performance also in the case where the filler is added as compared with the known compositions of the comparative examples. Furthermore, the photocuring polymerizate according to this invention suffered no substantial coloration, and were remarkably finer as compared with the comparative examples.

COMPARATIVE EXAMPLE 14

After pouring each of the compositions corresponding to Examples 10 and 17 respectively into the above-mentioned teflon tube, the upper surface of teflon tube was covered with an aluminum foil so that visible rays could not reach the poured mixture. The tube was disposed such that the upper surface of the poured mixture was at a 1 mm distance from the light irradiation surface and visible rays were irradiated for 3 minutes but no polymerization took place.

COMPARATIVE EXAMPLE 15

After pouring each of the compositions corresponding to Examples 10 and 17 respectively into the above-mentioned teflon tube, the upper surface of teflon tube was covered with an aluminum foil so that visible rays could not reach the poured mixture. Then, the tube was heated for 3 minutes at 60° C. but no polymerization took place.

EXAMPLES 24-30, COMPARATIVE EXAMPLES 16-18

A monomer filler mixture (paste) comprising:

Bis-GMA: 0.8 g

3G: 1.2 g

Silane modified quartz powder: 7.4 g

Silicon dioxide fine powder: 0.6 g

Photopolymerization initiator (Compounds and the addition amount listed in Table 6) was irradiated with visible rays for 60 seconds under the same procedures as those in Example 17. The thus obtained photopolymerization curing products were cut into cylindrical specimens of 4×6 mm, for which measurement was made to the compression strength, color change after one week exposure test to sunlight and color change after one week immersion test in water at 60° C.

Table 6 shows the kind and the amount of the photoinitiator, as well as the results of the above-mentioned measurement.

                                      TABLE 6                                      __________________________________________________________________________                                                Color change                                                                             Color change after                             Addition amount (%)                                                                       Compression strength                                                                      one week exposure                                                                        one week immersion                Photoinitiator                                                                              (based on monomer)                                                                        (kg/cm.sup.2)                                                                             to sunlight                                                                              in water at                                                                    60° C.             __________________________________________________________________________     Example 24                                                                             diphenyl disulfide +                                                                        3.0        2980       none      none                              camphorquinone                                                                              0.05                                                      Example 25                                                                             dibenzyl disulfide +                                                                        3.0        2770       "         "                                 camphorquinone                                                                              0.05                                                      Example 26                                                                             di-t-butyl disulfide +                                                                      3.0        2800       "         "                                 camphorquinone                                                                              0.05                                                      Example 27                                                                             trimethylene disulfide +                                                                    3.0        2660       none      none                              camphorquinone                                                                              0.05                                                      Example 28                                                                             p-(phenyl disulfanil)                                                                       3.0        2790       "         "                                 benzoic acid +                                                                 camphorquinone                                                                              0.05                                                      Example 29                                                                             diphenyl trisulfide +                                                                       3.0        2620       none      none                              camphorquinone                                                                              0.05                                                      Example 30                                                                             dibenzyl trisulfide +                                                                       3.0        2600       "         "                                 camphorquinone                                                                              0.05                                                      Comparative                                                                            camphorquinone                                                                              3.0        1460       extremely great                                                                          extremely great           Example 16                                                                     Comparative                                                                            N,N'-dimethylaniline +                                                                      3.0        1780       "         "                         Example 17                                                                             camphorquinone                                                                              0.05                                                      Comparative                                                                            5-butylbarbituric acid +                                                                    3.0        1800       great     great                     Example 18                                                                             camphorquinone                                                                              0.05                                                      __________________________________________________________________________

As apparent from Table 6, the compositions according to this invention have excellent mechanical strength and extremely high color stability as compared with the known compositions of the comparative examples.

Obviously, numerous modifications and variations of the present invention are possible in light of the above teachings. It is therefore to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described herein. 

What is claimed as new and desired to be secured by letters patent of the United States is:
 1. A photopolymerizable composition comprising:a vinylic monomer; a mixture of photoinitiators consisting of: (a) a polysulfide represented by the following formula:

    R.sub.4 --(S).sub.n --S--R.sub.4

where, n is an integer of from 0 to 10 and R₄ is a saturated C₁₋₂₀ alkyl group, a phenyl or benzyl group, each of which may be either unsubstituted or substituted with a carboxylic acid group at any position, and (b) camphorquinone, wherein the said mixture of photoinitiators is added in an amount of from 10⁻⁵ % by weight to 30% by weight based on the vinylic monomer.
 2. The photopolymerizable composition of claim 1, wherein the said photopolymerizable composition comprises a filler.
 3. The photopolymerizable composition of claim 1, wherein the said polysulfide comprises dimethyl disulfide, diethyl disulfide, dipropyl disulfide, dibutyl disulfide, diphenyl disulfide, dibenzyl disulfide, trimethylene disulfide, trimethyl trisulfide, diethyl trisulfide, dipropyl trisulfide, dibutyl trisulfide, diphenyl trisulfide, dibenzyl trisulfide, para-(phenyl disulfanil) benzoic acid or 3,3'-trithiodipropionic acid.
 4. The photopolymerizable composition of claim 1, wherein the said vinyl monomer is at least one selected from a monoethylenically vinylic monomer and a polyethylenically vinyl monomer.
 5. The photopolymerizable composition of claim 1, wherein the said monoethylenically vinylic monomer comprises styrene, acrylonitrile, vinyl acetate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, glycidyl acrylate or glycidyl methacrylate.
 6. The photopolymerizable composition of claim 4, wherein the said polyethylenically vinylic monomer comprises a compound represented by the following formula: ##STR6## where R₉ is a hydrogen atom or a methyl group and p is an integer of from 1 to
 20. 7. The photopolymerizable composition of claim 6, wherein the said polyethylenically vinylic monomer comprises ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, or polyethylene glycol dimethacrylate.
 8. The photopolymerizable composition of claim 4, wherein the said polyethylenically vinylic monomer comprises 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, glycerine diacrylate or glycerine dimethacrylate.
 9. The photopolymerizable composition of claim 4, wherein the said polyethylenically vinylic monomer is a compound represented by the following formula: ##STR7## wherein R₁₀ is a hydrogen atom or a methyl group and p is an integer of from 1 to
 20. 10. The photopolymerizable composition of claim 4, wherein the said polyethylenically vinylic monomer comprises bisphenol A diglycidyl acrylate or bisphenol A diglycidyl methacrylate.
 11. A photopolymerizable composition of claim 4, wherein the said polyethylenically vinylic monomer comprises trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate or pentaerythritol tetramethacrylate.
 12. The photopolymerizable composition of claim 1, wherein the said mixture of photoinitiators is added in an amount of from 10⁻³ % by weight to 15% by weight based on the vinylic monomer.
 13. The photopolymerizable composition of claim 1, wherein the said mixture of photoinitiators is added in an amount of from 10⁻¹ % by weight of 5% by weight based on the vinylic monomer.
 14. The photopolymerizable composition of claim 2, wherein the said filler comprises an oxide, a hydroxide, a chloride, a sulfate, a sulfite, a carbonate, a phosphate, or a silicate of a metal of groups I, II, III, IV and V of the Periodic Table and transition metals.
 15. The photopolymerizable composition of claim 2, wherein the said filler comprises silicon dioxide, quartz powder, aluminum oxide, barium sulfate, titanium oxide, talc, glass powder, glass beads, glass fibers, glass fillers containing barium salt and lead salt, silica gel, colloidal silica, carbon fibers, zirconium oxide or tin oxide. 